EP2059571B1 - Plasters and renders and paints, copolymer dispersions and their use - Google Patents

Abstract

Composition comprising a mineral filler, a pigment, colloidal silica and an aqueous polymer dispersion is new. The dispersion is produced by emulsion polymerization of a mixture comprising at least 40 wt.% of an alpha ,beta -unsaturated carboxylic acid ester, saturated carboxylic acid vinyl ester or vinylaromatic monomer, 0.1-10 wt.% of an alpha ,beta -unsaturated (di)carboxylic, sulfonic, phosphoric or phosphonic acid monomer, 0.5-15 wt.% of an alkoxysilyl-functional ethylenically unsaturated monomer and 0.1-10 wt.% of an ethylenically unsaturated monomer with an anionic or nonionic emulsifying group. Composition comprising a mineral filler, a pigment, colloidal silica and an aqueous polymer dispersion is new. The dispersion is produced by emulsion polymerization of a mixture comprising at least 40 wt.% of an alpha ,beta -unsaturated carboxylic acid ester, saturated carboxylic acid vinyl ester or vinylaromatic monomer (I), 0.1-10 wt.% of an alpha ,beta -unsaturated (di)carboxylic, sulfonic, phosphoric or phosphonic acid monomer (II), 0.5-15 wt.% of an alkoxysilyl-functional ethylenically unsaturated monomer (III), 0.1-10 wt.% of an ethylenically unsaturated monomer (IV) with an anionic or nonionic emulsifying group and 0-20 wt.% of other comonomers, where, instead or or in addition to copolymerization of (III), an alkoxysilyl-functional monomer with an amino, mercapto or epoxy group can be added in an amount of 0.5-15 wt.% after polymerization. An independent claim is also included for a polymer dispersion as above, except that (IV) is optional.

Description

The present invention relates to novel compositions containing selected polymer dispersions and colloidal silica and to the use of these compositions in plasters or in paints.

The use of aqueous polymer dispersions as binders in plasters or in paints is known to the person skilled in the art.

Also, aqueous compositions containing polymer dispersions and colloidal silica have been described frequently and for a wide variety of applications.

WO-A-00 / 23.533 describes coating compositions containing a hydrosol emulsion and colloidal silica. The hydrosol emulsion is prepared by neutralizing a synthetic resin emulsion with alkali, said resin emulsion being formed by dispersing particles of carboxyl and alkoxysilyl group-containing synthetic resins in water. Coating compositions for the production of coated papers are disclosed, but not cleaning or color formulations. To carry out the neutralization, these known synthetic resin emulsions must contain comparatively high proportions of copolymerized acidic monomers. When used as binders, these plastic emulsions would impart a lack of water resistance to the plaster or paint formulations because of their alkali solubility or swellability.

So is out of the EP-A-1,384,596 a coating composition for ink jet printing. This contains colloidal silica and a polymer dispersion obtained by emulsion polymerization of a radically polymerizable and a silyl group-containing monomer and a further monomer copolymerizable therewith in the presence of a surfactant. The polymer dispersion must have at least two glass transition temperatures. This can be accomplished by mixing different polymers with different glass transition temperatures or by multi-stage polymerization with different compositions of monomers. According to the embodiments, colloidal silica is added to the polymer dispersion after the emulsion polymerization. The resulting compositions are eminently suitable for ink-jet printing and, in addition to good service properties, are distinguished by increased gloss and weathering resistance of the printed substrates. The coating composition contains no fillers.

In the JP-A-2005-023,189 describes aqueous coating compositions from which formulate paints, which are characterized by good water resistance, weather resistance and resistance to organic bases. The compositions contain polymer dispersions prepared by emulsion polymerization, which are derived from (meth) acrylates and from ethylenically unsaturated carboxylic acid and optionally other monomers copolymerizable therewith. After the emulsion polymerization, alkoxysilanes which react with the emulsion polymer are added to the polymer dispersion. Thereafter, colloidal silica is added. The coating composition contains no fillers and the polymer dispersion contains no copolymerized emulsifier.

The JP-A-59-071,316 discloses a water-dispersible composition useful as an antifouling paint. During the emulsion polymerization of (meth) acrylates or vinylaromatics and copolymerizable silane monomers, colloidal silica is added. The polymer dispersion contains no copolymerized emulsifier.

From the JP-A-62-127.365 is a color formulation known that can be used indoors and outdoors and whose films are characterized by excellent permeability to moisture and high gloss. The Formulation contains an acrylate polymer which is emulsified together with colloidal silica. The dispersion is not produced by emulsion polymerization.

The JP-A-61-047,766 describes an additive for a material to be used indoors. This contains, in addition to a polyacrylate dispersion, a colloidal silica. The acrylate polymer has a low film-forming temperature. There is no indication of copolymers with alkoxysilyl groups.

In the JP-A-55-054,358 Coatings for the surface treatment of lightweight concrete parts are described. The compositions contain, in addition to an acrylic resin dispersion, colloidal silica, pigments and polyolefin glycol, calcium bicarbonate of selected particle diameter. There is no indication of copolymers with alkoxysilyl groups.

The JP-A-57-025,371 describes a composition for the treatment of building materials. This is prepared by mixing an aqueous resin or rubber suspension with colloidal silica. There is no indication of copolymers with alkoxysilyl groups.

In the JP-A-60-219.265 discloses a method of treating metal surfaces. In this case, an alkoxysilane-containing acrylate dispersion is used, which has been prepared by emulsion polymerization in the presence of colloidal silica. The polymer dispersion contains no copolymerized emulsifier.

The JP-A-02-117.977 describes a coating composition for building materials. In addition to a silane-containing first non-film-forming dispersion, a second film-forming dispersion is used. The polymer of the first dispersion has alkoxysilyl groups which bind colloidal silica. There is no evidence for the use of fillers.

In the JP-A-04-008,773 An antifouling paint is described. This is prepared by polymerization of alkoxysilane-containing acrylates in the presence of colloidal silica. The polymer dispersion contains no copolymerized emulsifier.

The JP-A-07-157.709 describes an aqueous coating composition for a wide variety of inorganic substrates. It forms coatings with high resistance to water and chemicals. The composition is characterized by emulsion polymerization of radically polymerizable monomers with copolymerizable alkoxysilanes. The result is a very finely divided copolymer with particle diameters of less than 100 nm, to which colloidal silica is added. The polymer dispersion contains no copolymerized emulsifier.

The JP-A-09-031,297 discloses a water-dispersible composition containing core-shell polymers characterized by good waterfastness of the films formed therefrom. The composition may contain colloidal silica. The shell of the polymer particles is derived from (meth) acrylates containing copolymerized alkoxysilane groups. The core of the polymer particles is derived from vinyl aromatic monomers and optionally from (meth) acrylates.

The JP-A-11-181.210 discloses a storage stable and curable composition. This is obtained by adding colloidal metal oxides other than colloidal silica to an aqueous dispersion of an alkoxysilane group-containing (meth) acylate copolymer prepared by microsuspension polymerization.

In the EP-A-989.168 For example, an aqueous coating composition is described. This is derived from a selected aqueous polymer dispersion which has been mixed with a selected amount of colloidal silica. The polymer is prepared by solution polymerization and then dispersed in water.

Although some of these documents describe the use of compositions containing colloidal silica in the construction field, there is still a need to improve these products.

It has now surprisingly been found that selected polymer dispersions containing colloidal silica and selected additives can be formulated into plasters or paints which are distinguished by excellent abrasion resistance, low soiling tendency, high water vapor permeability, good adhesion and good weathering stability. The compositions of the present invention can be made into plasters or paints that have a nanostructured surface and that differ from conventionally produced surfaces.

The object of the present invention is therefore the provision of formulations which can be used as plasters or paints in the interior and in particular in the exterior and which have the above-mentioned advantageous properties.

1. a) mineralischen Füllstoff, wobei der Anteil von Teilchen mit einem Durchmesser von mindestens 40 µm mindestens 40 Gew. % beträgt,
2. b) Pigment,
3. c) kolloidales Siliciumdioxid, und
4. d) wässerige Kunststoffdispersion, welche ein durch Emulsionspolymerisation hergestelltes Copolymer enthält, das sich ableitet von
   1. A) mindestens 40 Gew. %, bezogen auf die Gesamtmonomermenge, von Estern α, β-ungesättigter Carbonsäuren, Vinylestern gesättigter Carbonsäuren, vinylaromatischen Monomeren oder Kombinationen von zwei oder mehreren dieser Monomeren,
   2. B) 0,1 bis 10 Gew. %, bezogen auf die Gesamtmonomermenge, von α, β-ethylenisch ungesättigten Mono- und/oder Dicarbonsäuren, und/oder von α, β-ethylenisch ungesättigten Sulfonsäuren und/oder von α, β-ethylenisch ungesättigten Phosphorsäuren und/oder von α, β-ethylenisch ungesättigten Phosphonsäuren und/oder von Amiden von α, β-ethylenisch ungesättigten Mono- und/oder Dicarbonsäuren,
   3. C) 0,5 bis 15 Gew. %, bezogen auf die Gesamtmonomermenge, von ethylenisch ungesättigten Monomeren, welche mindestens eine Alkoxysilylgruppe aufweisen,
   4. D) 0,1 bis 10 Gew. %, bezogen auf die Gesamtmonomermenge, eines ethlyenisch ungesättigten oberflächenaktiven Monomeren enthaltend mindestens eine anionische und/oder nichtionische emulgierende Gruppe, und
   5. E) gegebenenfalls bis zu 20 Gew. %, bezogen auf die Gesamtmonomermenge, von mit den Monomeren der Gruppen A), B), C) und D) copolymerisierbaren sonstigen Monomeren, mit der Maßgabe, dass anstelle oder zusetzlich zur Copolymerisation des Monomeren C) nach der Emulsionspolymerisation 0,5 bis 15 Gew. %, bezogen auf die Gesamtmonomermenge, eines Monomeren zugegeben wird, das neben mindestens einer Alkoxysilylgruppe mindestens eine Amino-, Merkapto- oder Epoxidgruppe aufweist.

In a first embodiment, the invention relates to a composition comprising

1. a) mineral filler, the proportion of particles having a diameter of at least 40 μm being at least 40% by weight,
2. b) pigment,
3. c) colloidal silica, and
4. d) aqueous plastic dispersion containing a copolymer prepared by emulsion polymerization, which is derived from
   1. A) at least 40% by weight, based on the total monomer amount, of esters of α, β-unsaturated carboxylic acids, vinyl esters of saturated carboxylic acids, vinylaromatic monomers or combinations of two or more of these monomers,
   2. B) from 0.1 to 10% by weight, based on the total monomer amount, of α, β-ethylenically unsaturated mono- and / or dicarboxylic acids, and / or of α, β-ethylenically unsaturated sulfonic acids and / or of α, β-ethylenically unsaturated phosphoric acids and / or of α, β-ethylenically unsaturated phosphonic acids and / or of amides of α, β-ethylenically unsaturated mono- and / or dicarboxylic acids,
   3. C) 0.5 to 15% by weight, based on the total amount of monomer, of ethylenically unsaturated monomers which have at least one alkoxysilyl group,
   4. D) 0.1 to 10% by weight, based on the total amount of monomer, of an ethylenically unsaturated surface-active monomer containing at least one anionic and / or nonionic emulsifying group, and
   5. E) optionally up to 20% by weight, based on the total amount of monomers, of other monomers copolymerizable with the monomers of groups A), B), C) and D), with the proviso that instead of or additionally to the copolymerization of the monomer C) after the emulsion polymerization, 0.5 to 15% by weight, based on the total amount of monomer, of a monomer which has, in addition to at least one alkoxysilyl group, at least one amino, mercapto or epoxide group is added.

In this first embodiment of the compositions according to the invention, which are mainly used as plasters, the formulations contain, in addition to components b), c) and d), mineral fillers a) with a high proportion of coarse particles. Typically, the mineral filler a) in this embodiment contains at least 40% by weight of particles having a diameter of at least 40 μm.

Component a) is typically present in an amount of from 50 to 80% by weight, based on the total formulation, in this embodiment.

1. a) mineralischen Füllstoff, wobei der mittlere Durchmesser der Teilchen 1 bis 40 µm beträgt, sowie die oben definierten Komponenten b), c) und d).

The invention relates in a second embodiment containing a composition

1. a) mineral filler, wherein the average diameter of the particles is 1 to 40 microns, and the above-defined components b), c) and d).

In this second embodiment of the compositions according to the invention, which are mainly used as paints, the formulations contain, in addition to components b), c) and d), mineral fillers a) without coarse particle fractions. Typically, the average diameter of the particles (determined by sedimentation analysis according to DIN 66115) of the mineral filler a) in this embodiment is 2 to 40 μm.

Component a) is typically present in an amount of from 20 to 60% by weight, based on the total formulation, in this embodiment.

As components a) and b), the pigments and fillers known per se for use in coating compositions are used. These are solids on an inorganic and / or organic basis, which are preferably used as a powder. In the context of this description, pigments are understood to mean solids which have a refractive index of greater than or equal to 1.75. In the context of this description, fillers are understood as meaning solids which have a refractive index of less than 1.75.

Examples of mineral fillers are alkaline earth oxides, alkaline earth carbonates and / or silicate fillers, in particular calcium carbonate, mica, feldspar, kaolin, quartz flours and / or quartz granules fractions and marble granules and / or marble granules fractions.

Component b) can be any desired inorganic or organic pigments. As component b), coloring and opaque finely divided solids are used. Examples are listed below. Preferred pigments have a mean diameter for the primary grain of less than or equal to 1 .mu.m, preferably from 0.1 to 0.5 .mu.m, determined according to sedimentation analysis according to DIN 66115.

Examples of inorganic pigments are metal oxides, such as titanium dioxide, iron oxide or zinc oxide, in particular titanium dioxide.

Examples of organic pigments are phthalocyanines, in particular phthalocyanine blue, or diaryl pigments, azo pigments or quinacridone pigments.

Component b) in the first embodiment of the invention (plasters) is typically present in an amount of from 1 to 25% by weight, based on the total formulation, in particular in an amount of from 2 to 15% by weight.

Component b) in the second embodiment of the invention (paints) is typically present in an amount of from 1 to 50% by weight, based on the total formulation, in particular in an amount of from 2 to 20% by weight.

Component c) can be any colloidal silica. For the present invention, suitable colloidal silica is preferably an aqueous colloidal dispersion or suspension of ultrafine silica particles. The particle diameter of primary particles in this dispersion or suspension is preferably 2 to 100 nm, and the primary particles are spherical.

The colloidal silica c) used according to the invention is preferably an amorphous silica and is either of the anionic or of the cationic type (= anionic or cationic surface charges of the particles which are compensated by corresponding counterions). Dispersions in which the particles are stabilized by anionic surface charges and contain alkali metal or ammonium counterions, in particular sodium, potassium or ammonium counterions, are preferably used. Further, the colloidal silica may be monodispersed or polydispersed silica.

Colloidal silica is commercially available, for example under the trade names Klebosol ^{®, ®} or Köstrosol Levasil® ^®.

The colloidal silica is typically used in an amount of 5 to 200 parts by weight based on the amount of the copolymer. When the colloidal silica is used in an amount of 5 parts by weight or in a larger amount, the plaster or paint containing this plastic dispersion has the above-described advantageous properties.

If the colloidal silica is used in an amount of 200 parts by weight or in a smaller amount, the plaster or the paint according to the invention has good film-forming properties and is therefore well suited for use in the construction sector.

Component c) can already be added during the emulsion polymerization in the preparation of the aqueous polymer dispersion d). However, this embodiment is less preferred. Usually, component c) is added to the aqueous polymer dispersion after it has been prepared and / or during the preparation of the cleaning or color formulation. Particularly preferred is the addition of the colloidal silica after the preparation of the polymer dispersion.

In the modification of the aqueous polymer dispersion d) by addition of colloidal silica c), it has surprisingly been found that the compositions obtained are significantly different in comparison to formulations in which the colloidal silica is already present during the emulsion polymerization, namely by lower coagulum proportions Storage stability and the ability to adjust higher solids content.

In addition to components a) to d), preferred compositions additionally comprise water-soluble silicate e) and / or silicone resin f).

As water-soluble silicates e) it is possible to use all materials known per se to the person skilled in the art. Examples of these are water-soluble alkali water glass, in particular sodium or potassium water glass.

As silicone resins f) it is likewise possible to use all materials known per se to the person skilled in the art. Examples thereof are poly (dialkylsiloxanes), in particular poly (dimethylsiloxanes). These may be crosslinking or non-crosslinking systems.

Component e) is typically present in an amount of from 0 to 40% by weight, based on the total formulation, in particular in an amount of from 10 to 30% by weight.

Component f) is typically present in an amount of from 0 to 10% by weight, based on the total formulation, in particular in an amount of from 4 to 8% by weight.

The plastic dispersion d) used according to the invention is prepared by emulsion polymerization in a manner known per se. This produces aqueous dispersions of synthetic resin particles which, in addition to carboxyl groups and / or sulfonic acid groups and / or phosphoric acid groups and / or phosphonic acid groups, also have alkoxysilyl groups.

According to the invention, the plastics dispersion d) may be obtained by emulsion polymerization of at least one monomer of group A), preferably an ester of acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid and fumaric acid, with at least one monomer of group B) an ethylenically unsaturated carboxylic acid, with at least one monomer of group C), preferably an organoalkoxysilane with a radically polymerizable, unsaturated bond and with at least one monomer of group D). Alternatively, the plastic dispersion can also by emulsion polymerization of at least one monomer of group A) with at least one monomer of group B) and the group D) and by mixing the resulting copolymer with an organoalkoxysilane which contains at least one amino, mercapto or epoxide group instead of a free-radically polymerizable, unsaturated bond.

Performing emulsion polymerization by these methods results in obtaining a plastic dispersion in which the plastic particles containing a carboxyl group, an alkoxysilyl group and an emulsifying group are dispersed in water.

The selection of the monomer combinations used is carried out in such a way that the desired glass transition temperature (s) for the intended application are obtained. The person skilled in the selection criteria are known.

Usually, copolymers are prepared whose glass transition temperatures in the range of -50 to + 50 ° C, preferably -30 to + 30 ° C, are.

The glass transition temperatures are determined for purposes of the present description by differential scanning calorimetry (DSC) according to DIN 53765. For this, the sample was dried at 130 ° C for 1 hour, cooled and then heated. This is done at a heating rate of 10 K / minute.

According to the invention, the monomer of group A), namely a (meth) acrylate, a vinyl ester of a saturated carboxylic acid and / or a vinylaromatic monomer forms the skeleton of the plastic used for the preparation of the above-described plastic dispersion.

Preferred monomers of group A) are (meth) acrylic acid alkyl esters (ie alkyl esters of acrylic acid or methacrylic acid). Examples thereof are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and cyclohexyl acrylate. These alkyl esters may be used alone or in combination of two or more esters. In addition or instead of hydroxyl-containing or epoxy groups-containing (meth) acrylic acid alkyl esters can be used. If the alkyl (meth) acrylate used is a hydroxyl-containing or (meth) acrylic acid alkyl ester containing epoxide groups, the plastic disperse product prepared therewith also contains, in addition to the carboxyl and alkoxysilyl group, a hydroxyl group or an epoxide group.

Examples of hydroxyl group-containing (meth) acrylic acid alkyl esters include hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate and hydroxybutyl acrylate. These alkyl esters may be used alone or in combination of two or more esters.

Examples of epoxy group-containing (meth) acrylic acid alkyl esters include glycidyl methacrylate or glycidyl acrylate.

In addition to or instead of the (meth) acrylates, the main monomers used may be vinyl esters of saturated carboxylic acids. These are usually vinyl esters of saturated carboxylic acids having 1 to 18 carbon atoms.

Examples thereof are vinyl esters of carboxylic acids having 1 to 4 carbon atoms, such as vinyl formate, vinyl acetate, vinyl propionate, vinyl isobutyrate, vinyl pivalate and vinyl 2-ethylhexanoate; or vinyl esters of saturated, branched monocarboxylic acids having 9, 10 or 11 carbon atoms in the acid radical ( ^® Versatic acids); or vinyl esters of long-chain, saturated and unsaturated fatty acids, for example, vinyl esters of fatty acids having 8 to 18 carbon atoms, such as vinyl laurate and vinyl stearate; or vinyl esters of benzoic acid or p-tert-butylbenzoic acid and mixtures thereof, such as mixtures of vinyl acetate and a versatic acid or of vinyl acetate and vinyl laurate. Especially preferred is vinyl acetate.

In addition to or instead of the (meth) acrylates and / or the vinyl esters, the main monomers used may be vinylaromatic hydrocarbons. Examples of these are styrene, vinyltoluene and alpha-methylstyrene.

In addition to these main monomers, monomers of group B), namely free-radically polymerizable carboxylic acids, their amides, sulfonic acids, phosphoric acids, phosphonic acids or mixtures thereof are used for the preparation of the plastic dispersion.

Radical polymerizable carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids or mixtures thereof are preferably used as monomers of group B).

The monomers of group B) include those compounds which carry at least one carboxylic acid, carboxylic acid amide, sulfonic acid, phosphoric acid or phosphonic acid group in the direct vicinity of the double bond unit or which are connected to it via a spacer. Examples which may be mentioned are: ethylenically unsaturated C ₃ -C ₈ monocarboxylic acids, ethylenically unsaturated C ₄ -C ₈ dicarboxylic acids and their anhydrides or amides, and half esters of ethylenically unsaturated C ₄ -C ₈ dicarboxylic acids. Usually, the monomers of group B) have up to eight carbon atoms, in particular from 3 to 8 carbon atoms.

Preference is given to ethylenically unsaturated C ₃ -C ₈ monocarboxylic acids, such as acrylic acid, methacrylic acid and crotonic acid, and their anhydrides and amides; ethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid and citraconic acid, and their mono- or bis-amides and half esters with C ₁ -C ₁₂ -alkanols, preferably C ₁ -C ₄ -alkanols, for example monomethylmaleinate and mono-n-butyl maleate. Further preferred, ethylenically unsaturated, ionic monomers are ethylenically unsaturated sulfonic acids, in particular ethylenically unsaturated sulfonic acids having 2-8 carbon atoms, such as vinylsulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid, 2-acryloxyethanesulfonic acid and 2-methacryloxyethane-sulfonic acid, 3-acryloxy and 3-methacryloxypropanesulfonic acid, Vinylbenzenesulfonic acid, and ethylenically unsaturated phosphonic acids having 2-8 carbon atoms, such as vinylphosphonic acid.

In addition, in addition to or instead of the acids mentioned, their salts may also be used, preferably their alkali metal or ammonium salts and particularly preferably their sodium salts, such as, for example, the sodium salts of vinylsulfonic acid and 2-acrylamidopropanesulfonic acid.

Further examples of monomers of group B) are amides of ethylenically unsaturated carboxylic acids, in particular methacrylamide, acrylamide, crotonic acid amide, fumaric acid mono- or diamide, maleic acid mono- or diamide, itaconic mono- or diamide and citraconic mono- or diamide. In addition to the amides, it is also possible to use their N-functionalized derivatives, such as N-alkyl or N, N-dialkylamides. Preference is given to the non-functionalized derivatives.

In addition to the main monomers of group A) and the monomers of group B), monomers of group C), namely ethylenically unsaturated monomers which have at least one alkoxysilyl group, are preferably used for the preparation of the plastics dispersion. Instead of monomers of group C) or in addition to monomers of group C), a monomer may be added to the copolymer after the emulsion polymerization, which has at least one amino, mercapto or epoxide group in addition to at least one alkoxysilyl group.

Examples of organoalkoxysilanes are compounds having an ethylenically unsaturated, i. having a radical-polymerizable, unsaturated bond having at least one alkoxysilane group.

These are compounds which are incorporated into the copolymer during the polymerization; In addition, however, it is also possible to use organoalkoxysilanes which, in addition to the polymer, are present as a separate component in the dispersion.

1. a) ein Organofunktionelles Silan
   
   
   worin R¹ -(CH₂)_n-NH-R⁴, -(CH₂)_n-NH-[(CH₂)_m-NH]_o-R⁴ oder -(CH₂)_n-O-R⁵, -(CH₂)_n-CH=CH₂ oder -(CH₂)_n-S-R⁵ bedeutet,
   R² Wasserstoff, -(CH₂)_n-CH₃ oder R¹ ist,
   R³ Wasserstoff, -(CH₂)_n-CH₃ oder R² ist,
   R⁴ Wasserstoff, -(CH₂)_n-CH₃ oder -CO-(CH₂)_m-CH₃ bedeutet, und
   R⁵ Wasserstoff, -(CH₂-CH₂-O)_m-R⁴ oder
   
   ist, wobei n und m jeweils unabhängig voneinander eine ganze Zahl zwischen 0 und 12 und o eine ganze Zahl zwischen 0 und 5 ist.

The organoalkoxysilanes which can be used according to the invention preferably include compounds of the general formula I or II

1. a) an organofunctional silane
   
   
   wherein R ^{1 is} - (CH ₂ ) _n -NH-R ⁴ , - (CH ₂ ) _n -NH - [(CH ₂ ) _m -NH] _o -R ⁴ or - (CH ₂ ) _n -OR ⁵ , - ( CH ₂ ) _{n is} -CH = CH ₂ or - (CH ₂ ) _n -SR ⁵ ,
   R ^{2 is} hydrogen, - (CH ₂ ) _n -CH ₃ or R ¹ ,
   R ^{3 is} hydrogen, - (CH ₂ ) _n -CH ₃ or R ² ,
   R ^{4 is} hydrogen, - (CH ₂ ) _n -CH ₃ or -CO- (CH ₂ ) _m -CH ₃ , and
   R ^{5 is} hydrogen, - (CH ₂ -CH ₂ -O) _m -R ⁴ or
   
   where n and m are each independently an integer between 0 and 12 and o is an integer between 0 and 5.

Further preferred silanes are polyfunctional silanes. These include in particular compounds which, in addition to at least one silane group, have at least one primary, secondary or tertiary amino group, at least one Alkylthio group or sulfhydryl group or at least one epoxy group.

Particularly preferred compounds from this group are compounds of the formulas III, IV, V, VI, VII or VIII

(R ⁶ -Oh-Si (CH ₂ ) _p -NH- (CH ₂ ) _p -Si (OR ⁶ ) ₃ (III)

(R ⁶ -O) ₃ -Si (CH ₂ ) _p -N [- (CH ₂ ) _p -Si (OR ⁶ ] ₂ (IV)

(R ⁶ -O) ₃ -Si- (CH ₂ ) _p -S- (CH ₂ ) _p -Si- (OR ⁶ ) ₃ (V),

(R ⁶ -O) ₃ -Si- (CH ₂ ) _p -OR ⁷ (VI),

(R ⁶ -O) ₃ -Si- (CH ₂ ) _p -SR ⁸ (VII),

(R ⁶ -O) ₃ -Si- (CH ₂ ) _p -NR ⁹ R ¹⁰ (VIII),

in which R ^6, independently of one another, is hydrogen or C ₁ -C ₆ -alkyl, preferably methyl, ethyl or propyl,
R ^{7 is} hydrogen, C ₁ -C ₆ -alkyl or a glycidyl radical (1,2-epoxypropyl),
R ^{8 is} hydrogen or C ₁ -C ₆ -alkyl,
R ⁹ and R ¹⁰ independently of one another denote hydrogen or C ₁ -C ₆ -alkyl and p is an integer between 1 and 12.

Particularly preferred silanes of the formulas III, IV and V are the compounds:

(CH ₃ -O) ₃ -Si (CH ₂ ) _p -S- (CH ₂ ) _p -Si- (O-CH ₃ ) ₃ ,

(CH ₃ -CH ₂ -O) ₃ -Si- (CH ₂ ) _p -NH- (CH ₂ ) _p -Si- (O-CH ₂ -CH ₃ ) ₃ ,

(CH ₃ -O) ₃ -Si (CH ₂ ) _p -NH- (CH ₂ ) _p -Si- (O-CH ₃ ) ₃ ,

(CH ₃ -CH ₂ -O) ₃ -Si- (CH _{2) p} -N [- (CH _{2) p} -Si- (O-CH ₂ -CH _{3) 3] 2,}

(CH ₃ -O) ₃ -Si (CH ₂ ) _p -N [- (CH ₂ ) _p -Si (O-CH ₃ ) ₃ ] ₂

(CH ₃ -CH ₂ -O) ₃ -Si- (CH ₂ ) _p -S- (CH ₂ ) _p -Si- (O-CH ₂ -CH ₃ ) ₃ ,

(CH ₃ -O) ₃ -Si (CH ₂ ) _p -S- (CH ₂₎ p -Si (O-CH ₃ ) ₃ ,

wherein p has the meaning defined above.
Further preferred silanes used are di-, tri- or oligomeric silanes.

The silanes can be used as individual compounds or as mixtures.

• Silane des Handelsnamens Dynasylan^® (Degussa), des Handelsnamens Geniosil^® (Wacker) oder des Handelsnamens Silquest^® (GE Silicones).

Examples of silane compounds of the abovementioned type which are commercially available include:

• Silanes of the trade name Dynasylan ^® (Degussa), the trade name Geniosil ^® (Wacker) or trade name Silquest ^® (GE Silicones).

To organosilanes, which are incorporated into the polymer include ethylenically unsaturated monomers and containing alkoxysilane groups of the general formula R ¹¹ Si (CH _{3) 0-2} (OR ¹²⁾ _3-1, wherein R ^{11 has} the meaning CH ₂ = CR ¹³ - ( CH ₂ ) _0-1 or CH ₂ = CR ¹³ CO ₂ - (CH ₂ ) _1-3 , R ^{12 is} an unbranched or branched, optionally substituted alkyl radical having 1 to 12 C atoms, which may be interrupted by an ether group can, and R ^{13 is} hydrogen or methyl.

Preference is given to silanes of the formulas CH ₂ = CR ¹³ - (CH ₂ ) _0-1Si (CH ₃ ) _0-1 (OR ¹² ) _3-2 and CH ₂ = CR ⁹ CO ₂ - (CH ₂ ) ₃ Si (CH ₃ ) _0-1 (OR ⁸ ) _3-2 , wherein R ^{12 is} an unbranched or branched, optionally substituted alkyl radical having 1 to 12 C atoms and R ^{13 is} hydrogen or methyl.

Particularly preferred silanes are vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyl-di-n-propoxysilane, vinylmethyl-di-iso-propoxysilane, vinylmethyl-di-n-butoxy-silane, vinylmethyl-di-sec. butoxy-silane, vinylmethyl-di-tert-butoxy-silane, vinylmethyl-di- (2-methoxyisopropyloxy) -silane and vinylmethyldioctyloxy-silane.

Particularly preferred silanes of the formula CH ₂ = CR ¹³ - (CH ₂ ) _0-1 Si (OR ¹⁴ ) ₃ and CH ₂ = CR ² CO ₂ - (CH ₂ ) ₃ Si (OR ¹ ) ₃ , where R ^{14 is} a branched or unbranched alkyl radical having 1 to 4 carbon atoms and R ^{13 is} hydrogen or methyl.

Examples of these are γ- (meth) acryloxypropyl-tris- (2-methoxyethoxy) silane, γ- (meth) acryloxypropyl-tris-methoxy-silane, γ- (meth) acryloxypropyl-tris-ethoxy-silane, γ- (meth) acryloxypropyl-tris-n-propoxy-silane, γ- (meth) acryloxypropyl-tris-iso-propoxy-silane, γ- (meth) acryloxypropyl-silane tris-butoxy-silane, γ-acryloxypropyl-tris- (2-methoxyethoxy) -silane, γ-acryloxypropyl-tris-methoxy-silane, γ-acryloxypropyl-tris-ethoxy-silane, γ-acryloxypropyl-tris-n-propoxy- silane, γ-acryloxypropyl-tris-iso-propoxy-silane, γ-acryloxypropyl-tris-butoxy-silane, and vinyl-tris- (2-methoxyethoxy) -silane, vinyl-tris-methoxy-silane, vinyl-tris-ethoxy silane, vinyl-tris-n-propoxy-silane, vinyl-trisiso-propoxy-silane and vinyl-tris-butoxy-silane. If appropriate, the stated silane compounds can also be used in the form of their (partial) hydrolysates.

Particularly preferred silanes used are primary and secondary aminoalkylethoxysilanes, bis (3-triethoxysilylpropyl) amine, trifunctional propyltrimethoxysilane [NH ₂ - (CH ₂ ) ₂ -NH- (CH ₂ ) ₂ -NH- (CH ₂ ) ₃ -Si (OCH _{3 3} ], vinyltriethoxysilane [CH ₂ = CH-Si (OC ₂ H _s ) ₃ ], vinyltrimethoxysilane [CH ₂ = CH-Si (OCH ₃ ) ₃ ], 3-glycidyloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, oligomeric diaminosilane system , Glycidyltrimethoxy-functional silane, vinyltriethoxy-functional silane, glycidyltriethoxy-functional silane, vinyltris (2-methoxyethoxy) silane, (3-glycidoxypropyl) -trimethoxysilane, N- (2-aminoethyl) (3-aminopropyl) trimethoxysilane , (3-aminopropyl) triethoxysilane, N- (2-aminoethyl) (3-aminopropyl) -methyldimethoxysilane, (3-aminopropyl) -trimethoxysilane, (methacryloxymethyl) methyldimethoxysilane, (methacryloxymethyl) trimethoxysilane and / or (methacryloxy-methyl) methyldiethoxysilane.

In addition to the main monomers of group A) and the monomers of group B), the monomers of group C), monomers of group D), namely ethylenically unsaturated surface-active monomers containing at least one anionic and / or nonionic group, are used to prepare the polymer dispersion ,

These emulsifiers are surfactants which can be incorporated into the copolymer during the emulsion polymerization. Usually, the monomers of group D) have more than eight carbon atoms.

The monomers of group D) have at least one hydrophilic group, wherein the hydrophilic group may be nonionic, for example a polyglycol group, or may be anionic, for example a sulfate, sulfonate, phosphate or phosphonate group. Preferably, the monomers of group D) additionally have at least one hydrophobic group, where the hydrophobic group may be, for example, an alkyl, cycloalkyl, alkenyl, aryl or acyl group, and have at least 9 carbon atoms.

Preferably, the monomers of group D) have a vinyl group, an allyl group or a residue of an ethylenically unsaturated acid, such as an acrylic acid, methacrylic acid, crotonic acid, itaconic acid or maleic acid residue, and have at least 9 carbon atoms.

The monomers of group D) preferably have one to three nonionic or, in particular, anionic emulsifying groups. Particularly suitable emulsifying groups are polyalkylene glycol groups which are in particular anionically functionalized, for example with a sulphate or sulphonic acid group.

        CH₂=CH-O-C_uH_2u-O-(C₃H₆-O-)_v(C₂H₄-O-)_w-R³⁰     (XXX),

        CH₂=CH-CH₂-O-(C₃H₆-O-)_v(C₂H₄-O-)_w-R³⁰     (XXXI),

        CH₂=CH-CH₂-O-(C₃H₆-O-)_v(C₂H₄-O-)_w-SO₃M     (XXXII),

        [R³¹-O-(C₃H₆-O-)_v(C₂H₄-O-)_w]_t-R³²     (XXXIII),

worin R²⁰ und R²¹ unabhängig voneinander Wasserstoff oder C₁-C₄-Alkyl, vorzugsweise Wasserstoff oder Methyl, bedeuten,
R²² C₆-C₃₀-Alkyl, C₆-C₃₀-Alkenyl oder C₇-C₃₀-Alkylaryl ist, vorzugsweise C₈-C₂₄-Alkyl,
M ein Alkalimetallkation, ein Ammoniumion oder Wasserstoff bedeutet, vorzugsweise ein Natriumion oder ein Ammoniumion,
R²⁵, R²⁶ und R²⁷ unabhängig voneinander Wasserstoff, C₁-C₃₀-Alkyl, C₂-C₃₀-Alkenyl, Cycloalkyl, Aryl, oder Acyl bedeuten, vorzugsweise Wasserstoff, C₁-C₂₄-Alkyl oder C₂-C₄-Alkenyl,
n und m unabhängig voneinander ganze Zahlen von 1 bis 4 sind, vorzugsweise 2,
p eine ganze Zahl von 2 bis 4 bedeutet, vorzugsweise 2,
q eine ganze Zahl von 1 bis 100 bedeutet, vorzugsweise von 4 bis 20,
R²⁴ Wasserstoff, C₁-C₃₀-Alkyl, C₂-C₃₀-Alkenyl, Cycloalkyl, Aryl, oder Acyl bedeutet, vorzugsweise C₁-C₁₈-Alkyl,
r eine ganze Zahl von 0 bis 100 ist, vorzugsweise von 2 bis 20,
R²⁸ C₂-C₄-Alkenyl bedeutet, vorzugsweise Vinyl, Allyl oder Methylvinyl,
s eine ganze Zahl von 0 bis 100 ist, vorzugsweise von 2 bis 20,
t 1 oder 2 bedeutet,
R²⁹ C₁-C₃₀-Alkyl bedeutet, vorzugsweise C₁-C₄-Alkyl,
u eine ganze Zahl von 1 bis 20 ist, vorzugsweise von 2 bis 10,
v und w unabhängig voneinander ganze Zahlen von 0 bis 100 sind, vorzugsweise von 2 bis 20, wobei mindestens eine der Zahlen v oder w ungleich null sind,
R³⁰ Wasserstoff oder C₁-C₄-Alkyl, vorzugsweise Wasserstoff oder Methyl, bedeutet,
R³¹ ein Alkenylrest oder ein Carboxyalkenylrest mit 6-30 Kohlenstoffatomen ist, und
R³² Wasserstoff, C₁-C₄-Alkyl oder ein Rest der Formel PO_4-tM_3-t ist.Particularly preferred monomers are compounds of the general formulas X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII and XXXIII

CH ₂ = CH-OC _u H _2u -O- (C ₃ H ₆ -O-) _v (C ₂ H ₄ -O-) _w -R ³⁰ (XXX),

CH ₂ = CH-CH ₂ -O- (C ₃ H ₆ -O-) _v (C ₂ H ₄ -O-) _w -R ³⁰ (XXXI),

CH ₂ = CH-CH ₂ -O- (C ₃ H ₆ -O-) _v (C ₂ H ₄ -O-) _w -SO ₃ M (XXXII),

[R ³¹ -O- (C ₃ H ₆ -O-) _v (C ₂ H ₄ -O-) _w ] _t -R ³² (XXXIII),

in which R ²⁰ and R ²¹ independently of one another are hydrogen or C ₁ -C ₄ -alkyl, preferably hydrogen or methyl,
R ^{22 is} C ₆ -C ₃₀ -alkyl, C ₆ -C ₃₀ -alkenyl or C ₇ -C ₃₀ -alkylaryl, preferably C ₈ -C ₂₄ -alkyl,
M is an alkali metal cation, an ammonium ion or hydrogen, preferably a sodium ion or an ammonium ion,
R ²⁵ , R ²⁶ and R ²⁷ independently of one another are hydrogen, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, cycloalkyl, aryl or acyl, preferably hydrogen, C ₁ -C ₂₄ -alkyl or C ₂ - C ₄ alkenyl,
n and m are independently integers from 1 to 4, preferably 2,
p is an integer from 2 to 4, preferably 2,
q is an integer from 1 to 100, preferably from 4 to 20,
R ^{24 is} hydrogen, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, cycloalkyl, aryl, or acyl, preferably C ₁ -C ₁₈ -alkyl,
r is an integer from 0 to 100, preferably from 2 to 20,
R ^{28 is} C ₂ -C ₄ -alkenyl, preferably vinyl, allyl or methylvinyl,
s is an integer from 0 to 100, preferably from 2 to 20,
t is 1 or 2,
R ^{29 is} C ₁ -C ₃₀ -alkyl, preferably C ₁ -C ₄ -alkyl,
u is an integer from 1 to 20, preferably from 2 to 10,
v and w are independently integers from 0 to 100, preferably from 2 to 20, wherein at least one of the numbers v or w is non-zero,
R ^{30 is} hydrogen or C ₁ -C ₄ -alkyl, preferably hydrogen or methyl,
R ^{31 is} an alkenyl radical or a carboxyalkenyl radical having 6-30 carbon atoms, and
R ^{32 is} hydrogen, C ₁ -C ₄ -alkyl or a radical of the formula PO _{4 -t} M _3-t .

worin q, R²² und M die oben definierten Bedeutungen haben.Of these compounds enumerated above those are most preferably used which have at least 9 carbon atoms.
Very particular preference is given to using a compound of the formula XVa as the monomer of group D)

wherein q, R ²² and M have the meanings defined above.

In addition to the main monomers of group A), the monomers of group B), the monomers of group D) and, if appropriate, the monomers C), monomers of group E), namely other free-radically polymerizable monomers which are different from those used for the preparation of the plastics dispersion, can be used Different monomers of groups A) to D).

These may be very different groups of monomers.

The monomers of group E) include, for example, ethylenically unsaturated, nonionic functional monomers, such as water-soluble N-vinyl lactams, such as N-vinylpyrrolidone.

Also suitable as ethylenically unsaturated, nonionic functional monomers are nitriles of ethylenically unsaturated C ₃ -C ₈ -carboxylic acids, such as acrylonitrile and methacrylonitrile, and also adhesion-improving and crosslinking monomers. It is also possible to use C ₄ -C ₈ -conjugated dienes, such as 1,3-butadiene, isoprene and chloroprene, or aliphatic ethylenically unsaturated, optionally halogen-substituted hydrocarbons, such as ethylene, propylene, butylene, vinyl chloride or vinylidene chloride, as monomers.

Adhesion-enhancing monomers include both compounds having an acetoacetoxy moiety covalently attached to the double bond system as well as compounds with covalently bonded urea groups. The first-mentioned compounds include, in particular, acetoacetoxyethyl (meth) acrylate and allyl acetoacetate. The urea group-containing compounds include, for example, N-vinyl- and N-allyl-urea as well as derivatives of imidazolidin-2-one, such as N-vinyl- and N-allyl-imidazolidin-2-one, N-vinyloxy-ethylimidazolidin-2-one. on, N- (2- (meth) acrylamidoethyl) -imidazolidin-2-one, N- (2- (meth) -acryloxyethyl) imidazolidin-2-one, N- (2- (meth) acryloxy-acetamidoethyl) imidazolidine 2-one, and other known to the expert adhesion promoter based on urea or imidazolidin-2-one. To improve the adhesion, diacetoneacrylamide is also suitable in combination with a feed of adipic dihydrazide for dispersion.

As crosslinking monomers, both bifunctional and polyfunctional monomers can be used. Examples thereof are diallyl phthalate, diallyl maleate, triallyl cyanurate, tetraallyloxyethane, divinylbenzene, 1,4-butanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, divinyl adipate, allyl (meth) acrylate, vinyl crotonate, methylenebisacrylamide, hexanediol diacrylate, pentaerythritol diacrylate and trimethylolpropane triacrylate.

The copolymers used according to the invention are derived from at least 40% by weight, preferably from 50 to 90% by weight, of main monomers of group A). It may be a monomer or a mixture of different monomers of this group.

In addition, the copolymers used according to the invention are derived from 0.1 to 10% by weight, preferably from 1 to 6% by weight, particularly preferably from 1 to 4% by weight, of monomers of group B). It may be a monomer or a mixture of different monomers of this group.

Furthermore, the copolymers used according to the invention are derived from 1 to 15% by weight, preferably from 2 to 10% by weight, of alkoxysilane-containing monomers of group C). It may be a monomer or a mixture of different monomers of this group. The monomers of the group C) are optional, but their use is preferred. Instead of or in addition to the monomers of group C), it is possible to use amino-, mercapto- or epoxide-functionalized alkoxysilane-containing monomers.

The proportion of the monomers of group D) in the copolymers according to the invention is 0.1 to 10 wt.%, Preferably 0.5 to 5 wt.%, Particularly preferably 0.5 to 3 wt.%.

The proportion of monomers of group E) in the copolymers of the invention is 0 to 20 wt.%, Preferably 1 to 15 wt.%.

The quantities of the monomers are based on the total amount of monomers used in the emulsion polymerization and optionally in the addition. The proportion of copolymerized in the copolymer monomers generally corresponds to the added monomers.

Preference is given to using polymer dispersions derived from acrylates, methacrylates and / or vinyl esters of aliphatic carboxylic acids.

Preferred monomer mixtures of the monomers for the preparation of poly (meth) acrylates optionally together with vinyl esters are vinyl acetate / - butyl acrylate, vinyl acetate / dibutyl maleate, vinyl acetate / dibutyl fumarate, vinyl acetate / 2-ethylhexyl acrylate, vinyl acetate / ethene / butyl acrylate, vinyl acetate / ethene / dibutyl maleate , Vinyl acetate / ethene / dibutyl fumarate, vinyl acetate / ethene / 2-ethylhexyl acrylate, methyl methacrylate / butyl acrylate, methyl methacrylate / styrene / butyl acrylate, methyl methacrylate / 2-ethylhexyl acrylate, methyl methacrylate / styrene / 2-ethylhexyl acrylate, styrene / butyl acrylate, styrene / 2-ethyl-hexyl acrylate , Methyl methacrylate / isobutyl acrylate, methyl methacrylate / isopropyl acrylate.

Further preferred monomer mixtures of the monomers for the preparation of polyvinyl esters, if appropriate together with further functional monomers, are vinyl acetate / vinyl chloride / ethene, vinyl acetate / vinyl laurate / ethene, vinyl acetate / vinyl versatate / 2-ethylhexyl acrylate, vinyl acetate / vinyl laurate / ethene / vinyl chloride, Vinyl acetate / vinyl versatate / ethylene / vinyl chloride, vinyl versatate / ethene-vinyl chloride, vinyl acetate / vinyl versatate, vinyl acetate / vinyl versatate / ethene and vinyl acetate / ethene, with the combination of vinyl acetate / ethene being particularly preferred.

1. a) ein durch Emulsionspolymerisation hergestelltes Copolymer, das sich ableitet von
   1. A) mindestens 40 Gew. %, bezogen auf die Gesamtmonomermenge, von Vinylestern gesättigter Carbonsäuren, gegebenenfalls vinylaromatischen Monomeren und/oder gegebenenfalls Estern α, β-ungesättigter Carbonsäuren,
   2. B) 0,1 bis 10 Gew. %, bezogen auf die Gesamtmonomermenge, von α, βethylenisch ungesättigten Mono- und/oder Dicarbonsäuren, und/oder von α, β-ethylenisch ungesättigten Sulfonsäuren und/oder von α, β-ethylenisch ungesättigten Phosphorsäuren und/oder von α, β-ethylenisch ungesättigten Phosphonsäuren und/oder von Amiden von α, β-ethylenisch ungesättigten Mono- und/oder Dicarbonsäuren,
   3. C) 0,5 bis 15 Gew. %, bezogen auf die Gesamtmonomermenge, von ethylenisch ungesättigten Monomeren, welche mindestens eine Alkoxysilylgruppe aufweisen,
   4. D) gegebenenfalls bis zu 10 Gew. %, bezogen auf die Gesamtmonomermenge, eines ethlyenisch ungesättigten Monomeren, das eine anionische und/oder nichtionische emulgierende Gruppe enthält, und
   5. E) gegebenenfalls bis zu 20 Gew. %, bezogen auf die Gesamtmonomermenge, von mit den Monomeren der Gruppen A), B), C) und gegebenenfalls D) copolymerisierbaren sonstigen Monomeren, mit der Maßgabe, dass anstelle oder zusetzlich zur Copolymerisation des Monomeren C) nach der Emulsionspolymerisation 0,5 bis 15 Gew. %, bezogen auf die Gesamtmonomermenge, eines Monomeren zugegeben wird, das neben mindestens einer Alkoxysilylgruppe mindestens eine Amino-, Merkapto- oder Epoxidgruppe aufweist, und
2. b) kolloidales Siliciumdioxid
   sind neu und ebenfalls Gegenstand der vorliegenden Erfindung.

Containing aqueous plastic dispersion

1. a) a copolymer prepared by emulsion polymerization, which is derived from
   1. A) at least 40% by weight, based on the total monomer amount, of vinyl esters of saturated carboxylic acids, optionally vinylaromatic monomers and / or optionally esters of α, β-unsaturated carboxylic acids,
   2. B) from 0.1 to 10% by weight, based on the total monomer amount, of α, β-ethylenically unsaturated mono- and / or dicarboxylic acids, and / or of α, β-ethylenically unsaturated sulfonic acids and / or of α, β-ethylenically unsaturated phosphoric acids and / or of α, β-ethylenically unsaturated phosphonic acids and / or of amides of α, β-ethylenically unsaturated mono- and / or dicarboxylic acids,
   3. C) 0.5 to 15% by weight, based on the total amount of monomer, of ethylenically unsaturated monomers which have at least one alkoxysilyl group,
   4. D) optionally up to 10% by weight, based on the total amount of monomer, of an ethylenically unsaturated monomer which contains an anionic and / or nonionic emulsifying group, and
   5. E) optionally up to 20% by weight, based on the total monomer amount, of other monomers copolymerizable with the monomers of groups A), B), C) and optionally D), with the proviso that instead of or additionally to the copolymerization of the monomer C ) is added after the emulsion polymerization 0.5 to 15 wt.%, Based on the total amount of monomer, of a monomer having in addition to at least one alkoxysilyl group at least one amino, mercapto or epoxide group, and
2. b) colloidal silica
   are new and also the subject of the present invention.

In the compositions according to the invention, the polymer dispersion prepared by free-radical emulsion polymerization is particularly preferably used, which is a homopolymer or copolymer ("polyacrylate") derived from acrylate and / or methacrylate as main monomer or a homopolymer or copolymer derived from vinyl ester as main monomer ("polyvinyl ester "), preferably a polyacrylate or a polyvinyl ester having a glass transition temperature between -50 and + 50 ° C. The glass transition temperature of the polymer can be adjusted by suitable selection of the monomer combinations by a person skilled in the art.

The plastic dispersion used according to the invention can be additionally stabilized in addition to the copolymerized emulsifiers by protective colloids and / or by emulsifiers. These may already be present during the emulsion polymerization or added afterwards.

The protective colloids are polymeric compounds, for example having molecular weights of greater than 2000 g / mol, whereas the emulsifiers are low molecular weight compounds whose relative molecular weights are, for example, less than 2000 g / mol. These compounds are already added during the polymerization and may optionally also be added after the polymerization.

Examples of protective colloids are starch, gum arabic, alginates or tragacanth, methyl, ethyl, hydroxyethyl or carboxymethylcellulose or starch modified with saturated acids or epoxides and synthetic substances such as polyvinyl alcohol (with or without residual acetyl content) or partially esterified or acetalated or saturated Residues of etherified polyvinyl alcohol, as well as polypeptides such as gelatin, but also polyvinylpyrrolidone, polyvinylmethylacetamide or poly (meth) acrylic acid. Preference is given to polyvinyl alcohol.

The proportion by weight of such optionally present protective colloids, based on the total amount of the monomers used, is usually up to 15%.

In many cases, it is advantageous to use nonionic and / or anionic emulsifiers in the preparation of the dispersions, in addition to the protective colloids or instead of protective colloids.

Suitable nonionic emulsifiers are araliphatic and aliphatic nonionic emulsifiers, such as ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical C ₄ to C ₉ ), ethoxylates of long-chain alcohols (EO degree: 3 to 50, Alkyl radical: C ₈ to C ₃₆ ), as well as polyethylene oxide / polypropylene oxide block copolymers. Preferred are ethoxylates of long-chain alkanols (alkyl radical: C ₁₀ to C ₂₂ , average degree of ethoxylation: 3 to 50), and particularly preferably those based on native alcohols, Guerbet alcohols or oxo alcohols with a linear or branched C ₁₂ -C ₁₈ -alkyl radical and a degree of ethoxylation of 8 to 50, used.

Other suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208 ).

Suitable anionic emulsifiers are alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₈ ), alkyl phosphonates (alkyl radical: C ₈ to C ₁₈ ), sulfuric acid monoesters or phosphoric acid mono- and diem ethoxylated alkanols (EO degree: 2 to 50, alkyl radical : C ₈ to C ₂₂ ) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ to C ₉ ), of alkylsulfonic acids (alkyl radical: C ₁₂ to C ₁₈ ), of alkylarylsulfonic acids (alkyl radical: C ₉ to C ₁₈ ), sulfosuccinic monoesters and sulfosuccinic diesters of alkanols (alkyl group: C ₈ to C ₂₂ ) and ethoxylated alkanols (EO grade: 2 to 50, alkyl group: C ₈ to C ₂₂ ), and nonethoxylated and ethoxylated alkylphenols (EO grade: 3 to 50, alkyl: C ₄ to C ₉ ). In general, the emulsifiers listed are used as technical mixtures, wherein the information on the length of alkyl radical and EO chain on the respective maximum of the distributions occurring in the mixtures relates. Examples of said emulsifier classes are ^® Texapon K12 (sodium lauryl sulfate from Cognis), ^® Emulsogen EP (C ₁₃ -C ₁₇ -alkyl sulfonate from Clariant), ^® Maranil A 25 IS (sodium-n-alkyl- (C ₁₀ -C ₁₃ Benzenesulfonate from Cognis), ^® Genapol liquid ZRO (sodium C ₁₂ / C ₁₄ alkyl ether sulfate with 3 EO units from Clariant), ^® Hostapal BVQ-4 (sodium salt of a Nonylphenolethersulfats with 4 EO units from Clariant), aerosol MA 80 (sodium dihexyl sulfosuccinate from Cyctec Industries), aerosol A-268 (disodium isodecyl sulfosuccinate from Cytec Industries) and aerosol A-103 (disodium salt of a half ester of sulfosuccinic acid with an ethoxylated nonylphenol from Cytec Industries).

The amounts of the optionally used emulsifiers are within the usual limits. Overall, therefore, up to about 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the total amount of the monomers used to prepare the dispersions used. As a rule, mixtures of anionic and nonionic emulsifiers are used, but it is also possible to use anionic and nonionic emulsifiers alone for additional stabilization of the dispersions.

The aqueous polymer dispersions used according to the invention typically have solids contents of from 20 to 70% by weight, preferably from 30 to 65% by weight, and particularly preferably from 40 to 60% by weight.

Optionally, the polymer dispersions used according to the invention contain further additives customary per se.

As additives and other ingredients may be film-forming auxiliaries, such as white spirit, Texanol ^{®, ®} TXIB, butyl glycol, butyl diglycol, and Butyldipropylenglykol Butyltripropylenglykol; Plasticizers such as dimethyl phthalate, Disobutylphthalat, diisobutyl adipate, Coasol B ^® and 3060 ^® Plastilit; Wetting agents, such as AMP 90 ^{®, ®} TegoWet.280, Fluowet ^® PE; Thickeners, such as polyacrylates or polyurethanes, such as Borchigel L75 ^® and Tafigel PUR 60 ^®; Defoamers, eg mineral oil or silicone defoamers; UV stabilizers, such as Tinuvin 1130 ^®, subsequently added stabilizing emulsifiers or polymers such as polyvinyl alcohol or cellulose ethers, rheology modifying aids, for example, polyacrylate or polyurethane thickeners, and other additives and auxiliaries such as are customary for formulating plasters and paints, be used.

The polymer dispersion used according to the invention is prepared by free-radical emulsion polymerization. For the performance of the emulsion polymerization, any expedient and properly selected technique comes into consideration. Examples of methods of emulsion polymerization include a batch process in which a polymerization reactor is charged with water, an emulsifier surfactant and a monomeric component. To initiate the polymerization, the temperature of the mixture is raised, and the mixture is admixed with suitable additives, such as a polymerization initiator. In Monomerdosierverfahren the polymerization reactor water and emulsifier are supplied. The temperature of the mixture is raised and a monomeric component is added dropwise to the mixture. In the monomer emulsion metering method, prior to the dropwise addition of the monomer, the monomeric component is first emulsified with a surfactant serving as an emulsifier and with water, and the resulting emulsion is then added dropwise to the mixture.

The emulsion polymerization can thus be carried out in a batch process, in the feed process, in the combined batch / feed process or in the continuous process. In addition to the preparation of single-phase emulsion polymers, it is also possible to produce multiphase emulsion polymers. This is carried out by polymerization of several, preferably two different monomer combinations in successive stages. However, preference is given to using single-phase emulsion polymers.

Radical initiators used are, for example: hydrogen peroxide, benzoyl peroxide, cyclohexanone peroxide, isopropyl cumyl hydroperoxide, persulfates of Potassium, sodium and ammonium, peroxides of even saturated monohydric aliphatic carboxylic acids of chain length C ₈ -C ₁₂ , tertiary butyl hydroperoxide, ditertiary butyl peroxide, diisopropyl percarbonate, azoisobutyrodinitrile, acetylcyclohexanesulfonyl peroxide, tertiary butyl perbenzoate, tertiary butyl peroctoate, bis (3,5,5-trimethyl) hexanoyl peroxide, tertiary butyl perpivalate , Hydroperoxypinane, p-methane hydroperoxide. The aforementioned compounds can also be used within a redox system, with transition metal salts such as iron (II) salts or other reducing agents being included. Suitable reducing agents or regulators are alkali metal salts of oxymethanesulfinic acid, mercaptans of chain length C ₁₀ -C ₁₄ , butene-1-ol, 3-hydroxylamine salts, sodium dialkyldithiocarbamate, sodium bisulfite, ammonium bisulfite, sodium dithionite, diisopropylxanthogen disulfide, ascorbic acid, tartaric acid, isoascorbic acid, boric acid , Urea and formic acid are used.

Preferably, however, water-soluble persulfates, especially ammonium persulfate or sodium persulfate, are used to initiate the polymerization.

It is likewise preferred to use any chain transfer agents that are suitably selected from the known substances. Examples thereof include alcohols such as methanol, ethanol, propanol and butenol, aldehydes and ketones such as acetone, methyl ethyl ketone, cyclohexane, acetophenone, acetaldehyde, propionic aldehyde, n-butyl aldehyde, furfural and benzaldehyde and mercaptans such as dodecyl mercaptan, lauryl mercaptan, normal mercaptan, thioglycolic acid , Octyl thioglycolate and thioglycerol. Such chain transfer agents may be used alone or in combination of two or more thereof.

Any suitably and properly selected aqueous medium can be used for emulsion polymerization. Examples of aqueous media include water and aqueous alcoholic solutions. Water is preferred in terms of performance and cost. Water of all kinds, for example tap water or ion exchange water comes into consideration.

Protective colloid and / or emulsifier used for the stabilization can likewise either be completely initially charged at the start of the polymerization or partially charged and partially metered or completely metered in during the polymerization.

The polymerization temperature typically ranges from 20 to 120 ° C, preferably from 30 to 110 ° C, and most preferably from 45 to 95 ° C.

After completion of the polymerization, a further, preferably chemical aftertreatment, in particular with redox catalysts, such as, for example, combinations of the abovementioned oxidizing agents and reducing agents, may be added for demonomerization. Furthermore, in a known manner, for example, by physical Entmonomerisierung, d. H. distillative removal (in particular via steam distillation) or by stripping with an inert gas, residual monomer present be removed. Particularly effective is a combination of physical and chemical methods, which allows a lowering of the residual monomers to very low levels (<1000 ppm, preferably <100 ppm.

The compositions according to the invention can easily be prepared by simply mixing the intended amounts of the individual components by means of a conventional stirrer or the like. In the compositions of the present invention, the plastic dispersion containing an acid group and an alkoxysilyl group and having various excellent physical properties is associated with the colloidal silica. Therefore, the compositions are characterized by stable physical properties and excellent use properties.

The compositions of the invention can be used in the construction sector, namely as plasters or as paints. These compositions are particularly preferably used as plasters, facade paints and Dachsteinfarben. These uses are also the subject of the present invention. Particularly preferred plasters and paints used according to the invention are stabilized by using nonionic emulsifiers as dispersants, for example with the products Surfynol 104 H, Additiol VXW 6208, Nusoperse 2006 and Nuosperse 2008.

Yet another object of the present invention is the use of plastic dispersions comprising an aqueous polymer dispersions prepared by free radical emulsion polymerization derived from the above-described monomers A), B), C), D) and optionally E) and colloidal silica in plasters or in paints.

The following examples serve to illustrate the invention. The parts and percentages given in the examples are by weight unless otherwise stated.

Examples 1 to 5

Working instructions for the preparation of the copolymer dispersion of Example 1 which can be used according to the invention

Into a 2.5 liter reactor equipped with anchor stirrer and condenser, a template according to Table 1 was added and heated to 80 ° C. Subsequently, 5% of the monomer dispersion described in Table 1 was added as quickly as possible and immediately thereafter a solution of 0.38 g of potassium peroxodisulfate in 18 g of water was added. After 15 minutes of polymerization, the remainder of the monomer emulsion and a solution of 1.54 g of potassium peroxodisulfate in 72 g of water were added separately over 4 hours while maintaining the temperature at 80 ° C. Thirty minutes after completion of the addition, 9.36 g of a 12.5% aqueous ammonia solution was added to the reactor and the temperature was maintained at 80 ° C for an additional hour. The batch was then cooled to room temperature and 1047.46 g of a colloidal silica dispersion (solids content: 41%;
Particle size: 25 nm, pH: 9.9).

The dispersions of Examples 2 to 5 were prepared analogously to the above procedure. Details of the experiment are shown in Table 1 below. In Comparative Examples 2 and 4, no colloidal silica was added. Table 2 shows some properties of the resulting dispersions. Table 1: Composition of the polymer dispersions prepared example 1 Example 2 Example 3 Example 4 Example 5 template Water (g) 308 308 308 308 308 Emulsifier D) ¹⁾ (g) 25.3 25.3 0.6 0.6 0.6 monomer Water (g) 299 408 299 324 341.7 Emulsifier D) ¹⁾ (g) 13.1 13.1 37.7 37.7 37.7 Methacrylic acid (g) 18.9 18.9 18.9 18.9 18.9 Methyl methacrylate (g) 295.8 295.8 295.8 295.8 295.8 Butyl acrylate (g) 304.2 304.2 304.2 304.2 304.2 Vinyltriethoxysilane (g) 13.1 13.1 13.1 13.1 13.1 Subsequently administer Colloidal silica (g) 1,047.5 - 1030 - 515 Water (g) - - - 78 - ¹⁾ Poly (oxy-1,2-ethanediyl) -alpha-sulfo-omega [4-nonyl-2- (1-propenyl) -phenoxy] (branched) ammonium salt Example no. Solids content (%) Viscosity according to Brookfield mPas (23 ° C, 20 rpm) PH value Particle size (nm) ²⁾ 1 45.2 1290 8.4 108 2 45.0 9200 7.8 78 3 45.0 80 8.5 139 4 44.7 370 8.4 126 5 44.9 100 8.4 151 ²⁾ average particle diameter (weight average) determined by dynamic light scattering

• 242 GT Wasser
• 242 GT 1,2-Propylenglykol
• 52 GT Dispex GA 40 (Handelsprodukt der Fa. Ciba Speciality Chemicals;
  Dispergiermittel enthaltend Ammoniumsalz eines Acrylsäurecopolymerisats)
• 10 GT AMP 90 (2-Amino-2-Methyl-I-Propanol)
• 20 GT Entschäumer BYK 022
• 20 GT Biozid Mergal K7
  wurden gemischt, unter Rühren 740 GT Titandioxid Kronos 2190 eingetragen und anschließend mit einem Dissolver mit mindestens 14 m/s Umfangsgeschwindigkeit an der Zahnscheibe für 20 Minuten dispergiert. Nach dem Abkühlen der Pigmentanreibung wurden
• 185 GT Bindemittel (Dispersion)
• 33 GT Pigmentanreibung unter Rühren gemischt.

With the dispersions of Examples 1 and 2, colors were prepared according to the following recipe (GT = parts by weight):

• 242 GT water
• 242 GT 1,2-propylene glycol
• 52 GT Dispex GA 40 (commercial product from Ciba Specialty Chemicals;
  Dispersant containing ammonium salt of an acrylic acid copolymer)
• 10 GT AMP 90 (2-amino-2-methyl-1-propanol)
• 20 GT defoamer BYK 022
• 20 GT biocide Mergal K7
  were mixed, 740 GT titanium dioxide Kronos 2190 entered with stirring and then dispersed with a dissolver with at least 14 m / s peripheral speed on the toothed wheel for 20 minutes. After cooling the pigment preparation were
• 185 GT binder (dispersion)
• 33 pbw pigment slurry mixed with stirring.

• 1,5 GT Ammoniak (25%ig)
• 15,3 GT 1,2-Propylenglykol
• 3,7 GT Texanol (Handelsprodukt der Fa. Eastman Chemicals; Lösungsmittel enthaltend 2,2,2-Trimethyl-1,3-pentandiol-monoisobutyrat), und am Ende die Verdickermischung
• 8,3 GT Mowilith LDM 7002 (ca. 18%ig in Wasser) zugegeben.

During further stirring at moderate stirring speed were

• 1.5 GT ammonia (25%)
• 15.3 parts of 1,2-propylene glycol
• 3.7 GT Texanol (commercial product from Eastman Chemicals; containing 2,2,2-trimethyl-1,3-pentanediol monoisobutyrate), and finally the thickener mixture
• 8.3 GT Mowilith LDM 7002 (about 18% in water) was added.

With the dispersions of Examples 1 and 2 plasters were prepared according to the recipe given in Table 3 (GT = parts by weight): Table 3: Plaster ingredients parts by weight water 53.5 Thickener (polyacrylate) 1.5 Mowiplus XW 330, dispersant 3.0 Calgon N, 10%, wetting agent 6.0 Caustic soda, 10% 2.0 Agitan, defoamer 2.0 Dispersion ³⁾ 140.0 Titanium dioxide Kronos 2160 20.0 China Clay B 20.0 Calcium carbonate, Omyacarb 40 GU 150.0 Calcium carbonate, Omyacarb 130 GU 170.0 Calcilite 0.1-0.5 100.0 Calcilite 1.5-2.0 300.0 white spirit 4.0 butyldiglycolacetate 6.0 polyethylene 2.0 ³⁾ according to Examples 1 and 2

The components listed in Table 3 were made into a plaster in a stirred vessel.

Application engineering investigations blocking resistance

To test the blocking resistance, opacity cards of BYK Malinckrodt or Morest were coated with 50 μm wet film thickness. After drying for 24 hours, two sham cards with their coated side were placed on top of each other and subjected to 3.1 × 10 ⁴ N / m ^{2 for} 2 hours at room temperature. Then the force was determined to separate the cards again.

Cross-cut test

Glass plates were coated with 200 μm wet film thickness and dried at 23 ° C for 24 hours at 50% humidity. The cross-cut test was carried out in accordance with DIN 51151.

blister test

The colors were applied well on a glass plate with a painter's roller. After a drying time of 24 hours, a second coat was applied in the same way. The size of the paint surface was 20 × 30 cm. After a 24-hour drying of the second coat, the glass plates were placed with the coated side down on a water bath (blister bath). The temperature of the water bath was 50 ° C. The distance of the water surface to the sample plate was 15 cm and the test plates covered the water bath over the entire surface. After 8 hours of loading, the test plates were removed from the blister bath and placed vertically at room temperature for drying. The drying time was at least 2 hours. The evaluation was carried out visually on the dried sample. Liability and blistering were assessed.

Determination of soiling tendency with dirt suspensions

The color to be examined was applied using a box doctor blade (300 μm) to fiber cement panels, Eterplan, 300 x 150 x 4 mm. The to be examined Plaster was applied to the Eterplan plates and dried for 24 hours at room temperature.

The test medium used was a soil suspension consisting of 17% carbon black, 70% Japanese standard dust No. 8 and 13% special pitch No. 5 (Worlee). The triturated standard soil powder (1.0 g) was stirred in butyl glycol (1.0 g) and suspended in 998.0 g of water.

The test panels were placed on a base at an angle of 60 °. 500 ml of the soil suspension were dropped uniformly over the test panel in a circuit with a pump for 30 minutes. Thereafter, it was dried at 50 ° C for 24 hours. Subsequently, the L value was determined according to DIN 5033. This cycle was repeated five times and the L value determined each time. Each new cycle used a new soil suspension. In the determination of the L value, the measurement was carried out at four points of the surface and the mean value was determined therefrom. The difference of the L value was determined per cycle (L value, white = at the beginning of the cycle, L value, black = at the end of the cycle).

Results of the application tests soiling

When determining the soiling tendency with soil suspensions, a plaster containing the dispersion of Example 1 showed a difference in the L values (white-black) of 9.8. On the other hand, a plaster containing the dispersion of Comparative Example 2 had a difference in L values (white-black) of 16.2.

After weathering of the samples for 3 months, a plaster containing the dispersion of Example 1 showed a difference in the L values of 2.5. On the other hand, a weather-exposed plaster containing the dispersion of Comparative Example 2 had a difference in L values of 3.5. After weathering of the samples for 6 months, a plaster containing the dispersion of Example 1 showed a difference in L values of 3.9. On the other hand, a weather-exposed plaster containing the dispersion of Comparative Example 2 had a difference in L values of 5.5.

crosshatch

In the cross hatch test, a paint containing the dispersion of Example 1 did not show any broken cut edges (rating 0). On the other hand, a paint containing the dispersion of Comparative Example 2 showed breakouts at 15-35% of the cut edges (Rank 3).

blocking resistance

In the blocking resistance test, a paint containing the dispersion of Example 1 showed a blocking resistance of 40 g / 6.25 cm ² . On the other hand, a paint containing the dispersion of Comparative Example ² showed a blocking resistance of 1300 g / 6.25 cm ² .

blister test

In the blister test, a paint containing the dispersion of Example 1 showed no blistering and adhered well. On the other hand, a paint containing the dispersion of Comparative Example 2 showed a strong blistering and only an unsatisfactory adhesion.

Examples 6 to 8

• Beispiel 6: 65 Teile Paste und 35 Teile Dispersion gemäß Beispiel 3.
• Vergleichsbeispiel 7: 65 Teile Paste und 35 Teile Dispersion gemäß Beispiel 4.
• Beispiel 8: 65 Teile Paste und 35 Teile Dispersion gemäß Beispiel 5.

It was first prepared a paste according to the recipe in the table below. ingredients parts by weight water 140.0 Thickener (Tylose) 2.0 Agitan 281 4.0 Dispersant, Lopon 895 4.0 Calgon N, 10% 5.0 Titanium dioxide Kronos 2160 200.0 Calcium carbonate, Omyacarb 5 GU 210.0 Micro Talc AT1 40.0 China Clay B 20.0 Ammonia, conc. 2.0 butyldiglycolacetate 17.0 Tafigel PUR 40 1: 9 in water 6.0 To prepare the example colors 6, 7 and 8, 65 parts of the paste were stirred together with 35 parts of the dispersion as follows until a homogeneous color had been obtained:

• Example 6: 65 parts of paste and 35 parts of dispersion according to Example 3.
• Comparative Example 7 65 parts of paste and 35 parts of dispersion according to Example 4.
• Example 8: 65 parts of paste and 35 parts of dispersion according to Example 5.

In the FIGS. 1 to 3 are SEM photographs of surfaces of paints of the paints containing the dispersion of Example 6 ( FIG. 1 ), the dispersion of Example 8 ( FIG. 2 ) and the dispersion of Example 7 ( FIG. 3 ).

SEM samples were prepared as follows: The colors were coated on slides and dried at room temperature. Thereafter, the surfaces were examined in a scanning electron microscope with a magnification of 100,000 times. The inks according to the invention show a clear nanostructure on the color surface ( Figures 1 and 2 ) which differ significantly from the comparative color ( FIG. 3 ) difference.

Examples 9 and 10: Preparation of a vinyl acetate / ethylene copolymer dispersion with and without colloidal silica

• 22000 g Wasser, 86 g Natriumacetat, 1440 g einer 70 Gew. %-igen wässrigen Lösung eines Oxoalkylethoxylats mit 28 Mol Ethylenoxid, 2160 g einer 10 Gew. %-igen wässrigen Polyvinylalkohollösung (Viskosität der 4 Gew. %-igen wässrigen Lösung 18 mPa*s), 1127 g einer 15 Gew. %-igen Natriumlaurylsulfatlösung, 577 g einer 30 Gew. %-igen wässrigen Natriumvinylsulfonatlösung und 8 g einer 1 Gew. %-igen wässrigen Lösung von Fe-II(SO₄) x 7 H2O. Der pH-Wert der Lösung betrug 7,2. Die Apparatur wurde von Luftsauerstoff befreit und es wurde Ethylen in die Apparatur gedrückt. Bei 20 bar Ethylendruck wurden 1500 g Vinylacetat eindosiert. Es wurde auf 60° C Innentemperatur erhitzt und dabei der Ethylendruck auf 40 bar gesteigert. Nun wurden 10% einer Lösung aus 27,1 g Brüggolit C in 2000 g Wasser eindosiert. Anschließend wurden 10% einer Lösung aus 27,1 g t-Butylhydroperoxid in 2000 g Wasser zudosiert bei einer Innentemperatur von 60° C und es wurde zur Abführung der Reaktionswärme gekühlt. Eine Mischung aus 28800 g Vinylacetat und 70 g Vinyltrimethoxysilan (VTM) und die restlichen 90 % der Reduktions- und Initiatorlösung wurden anschließend, wobei der Ethylendruck auf 40 bar gehalten wurde, bis 4135 g Ethylen im Reaktor waren, zudosiert. Danach wurde eine Lösung aus 36 g Natriumpersulfat in 600 g Wasser zudosiert und die Innentemperatur auf 80° C erhöht und 1 Stunde bei dieser Temperatur gehalten. Unter Rühren wurde anschließend der Großteil des nicht umgesetzten Ethylens ausgegast und es wurden 2 l Wasser zugegeben. Dann wurden unter Anlegen von Vakuum innerhalb von 2 Stunden 2 l Wasser abdestilliert, wodurch der Restvinylacetatgehalt der Dispersion auf 0,05 Gew. %, bezogen auf die Dispersion, reduziert wurde. Durch Wiederholung des Trennverfahrens wurde ein Restvinylacetatgehalt von 0,012 Gew. % erreicht. Anschließend wurde der Ansatz auf Raumtemperatur abgekühlt. Es wurde eine Dispersion eines Copolymeren erhalten, die 12 Gew. % von Ethylen abgeleiteten Einheiten, 0,5 Gew. % an von Na-Vinylsulfonat abgeleiteten Einheiten, 0,2 Gew. % an von Vinyltrimethoxysilan abgeleiteten Einheiten aufwies. Der Gehalt an Polyvinylalkohol betrugt 0,6 Gew. %, bezogen auf den Feststoffgehalt; der Gehalt an Oxoalkylethoxilat betrug 3 Gew. %, bezogen auf den Feststoffgehalt. Der Feststoffgehalt der Dispersion betrug 54%.

In a pressure apparatus with stirrer, jacket heating and metering pumps, an aqueous solution consisting of the following constituents was added:

• 22000 g of water, 86 g of sodium acetate, 1440 g of a 70 wt.% Aqueous solution of a Oxoalkylethoxylats with 28 moles of ethylene oxide, 2160 g of a 10 wt.% Aqueous polyvinyl alcohol solution (viscosity of 4 wt.% Aqueous solution 18 mPa * s), 1127 g of a 15% strength by weight sodium lauryl sulfate solution, 577 g of a 30% strength by weight aqueous sodium vinylsulfonate solution and 8 g of a 1% strength by weight aqueous solution of Fe-II (SO ₄ ) × 7H 2 O. The pH of the solution was 7.2. The apparatus was freed of atmospheric oxygen and ethylene was forced into the apparatus. At 20 bar ethylene pressure 1500 g of vinyl acetate were metered. It was heated to 60 ° C internal temperature while the ethylene pressure increased to 40 bar. Now 10% of a solution of 27.1 g Brüggolit C in 2000 g of water were metered. Subsequently, 10% of a solution of 27.1 g of t-butyl hydroperoxide in 2000 g of water was added at an internal temperature of 60 ° C and it was cooled to dissipate the heat of reaction. A mixture of 28,800 g of vinyl acetate and 70 g of vinyltrimethoxysilane (VTM) and the remaining 90% of the reducing and initiator solution were then metered in, keeping the ethylene pressure at 40 bar until 4135 g of ethylene were in the reactor. Thereafter, a solution of 36 g of sodium persulfate in 600 g of water was added and the internal temperature increased to 80 ° C and held for 1 hour at this temperature. With stirring, most of the unreacted ethylene was then outgassed and 2 liters of water were added. Then 2 l of water were distilled off under the application of vacuum within 2 hours, whereby the residual vinyl acetate content of the dispersion was reduced to 0.05% by weight, based on the dispersion. By repeating the separation process, a residual vinyl acetate content of 0.012 wt.% Was achieved. Subsequently, the batch was cooled to room temperature. A dispersion was obtained of a copolymer containing 12% by weight of units derived from ethylene, 0.5% by weight of units derived from Na vinylsulfonate, 0.2% by weight of units derived from vinyltrimethoxysilane. The content of polyvinyl alcohol was 0.6% by weight based on the solids content; the content of Oxoalkylethoxilat was 3 wt.%, Based on the solids content. The solids content of the dispersion was 54%.

For the preparation of Comparative Example 9, the dispersion was diluted with 1896 g of water. The solids content was 51%.

To prepare Inventive Example 10, 8752 g of a colloidal silica dispersion (solids content: 40%) were added to the dispersion over 30 minutes. The solids content was 51%.

To test the blocking resistance, glass slides were coated with a wet film thickness of 300 μm. After 24 hours of drying, two coated slides were placed one on top of the other with their coated side and loaded by their own weight for 2 hours at room temperature. Then the force was determined to separate the slides again.

For Comparative Example 9, a block strength of 2444 g / 6.25 cm ^{2 was} determined. The example according to the invention showed a significantly better blocking resistance of 609 g / 6.25 cm ² .

Claims (22)

1. A composition containing

   a) mineral filler, the proportion of particles having a diameter of at least 40 µm being at least 40% by weight, or mineral filler, the mean diameter of the particles being from 1 to 40 µm, the filler having a refractive index less than 1.75,

   b) pigment which has a refractive index greater than or equal to 1.75,

   c) colloidal silica and

   d) aqueous plastics dispersion which contains a copolymer which is prepared by emulsion polymerization and is derived from

   A) at least 40% by weight, based on the total amount of monomer, of esters of α,β-unsaturated carboxylic acids, vinyl esters of saturated carboxylic acids, vinylaromatic monomers or combinations of two or more of these monomers,

   B) from 0.1 to 10% by weight, based on the total amount of monomers, of α,β-ethylenically unsaturated mono- and/or dicarboxylic acids and/or of α,β-ethylenically unsaturated sulfonic acids and/or of α,β-ethylenically unsaturated phosphoric acids and/or of α,β-ethylenically unsaturated phosphonic acids and/or of amides of α,β-ethylenically unsaturated mono- and/or dicarboxylic acids,

   C) from 0.5 to 15% by weight, based on the total amount of monomers, of ethylenically unsaturated monomers which have at least one alkoxysilyl group,

   D) from 0.1 to 10% by weight, based on the total amount of monomers, of an ethylenically unsaturated surface-active monomer containing at least one anionic and/or nonionic emulsifying group and

   E) optionally up to 20% by weight, based on the total amount of monomers, of other monomers copolymerizable with the monomers of groups A), B), C) and D), with the proviso that,
   instead of or in addition to the copolymerization of the monomer C), from 0.5 to 15% by weight, based on the total amount of monomers, of a monomer which has at least one amino, mercapto or epoxide group in addition to at least one alkoxysilyl group is added after the emulsion polymerization.
2. The composition as claimed in claim 1, which additionally contains e) water-soluble silicate and/or f) silicone resin.
3. The composition as claimed in either of claims 1 and 2, which contains a mineral filler a), the proportion of particles having a diameter of at least 40 µm being at least 40% by weight, and this filler is present in an amount of from 50 to 80% by weight, based on the total formulation.
4. The composition as claimed in either of claims 1 and 2, which contains a mineral filler a), the mean diameter of the particles being from 1 to 40 µm, and this filler is present in an amount of from 20 to 60% by weight, based on the total formulation.
5. The composition as claimed in any of claims 1 to 4, wherein the mineral filler a) is calcium carbonate, quartz and/or a silicate filler, in particular mica or feldspar.
6. The composition as claimed in any of claims 1 to 5, wherein the pigment b) is titanium dioxide, iron oxide, zinc oxide and/or a phthalocyanine pigment and is present in an amount of from 1 to 50% by weight, based on the total formulation.
7. The composition as claimed in any of claims 1 to 6, wherein the colloidal silica c) has a mean diameter of from 2 to 100 nm and is present in an amount of from 5 to 200% by weight, based on the amount of the copolymer.
8. The composition as claimed in any of claims 2 to 7, wherein the water-soluble silicate is alkali waterglass, in particular sodium waterglass or potassium waterglass.
9. The composition as claimed in any of claims 2 to 8, wherein the silicone resin is a polydimethylsiloxane.
10. The composition as claimed in any of claims 1 to 9, wherein component A) is an acrylate and/or a methacrylate, optionally in combination with styrene.
11. The composition as claimed in any of claims 1 to 9, wherein component A) is a vinyl ester of a saturated carboxylic acid having one to four carbon atoms, preferably vinyl acetate.
12. The composition as claimed in any of claims 1 to 11, wherein component B) is acrylic acid, methacrylic acid or vinylsulfonic acid.
13. The composition as claimed in any of claims 1 to 12, wherein component C) is vinyltrialkoxysilane, preferably vinyltrimethoxy- or vinyltriethoxysilane.
14. The composition as claimed in any of claims 1 to 13, wherein component D) is derived from compounds of the formulae X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII and XXXIII

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    

    
    
            CH₂=CH-O-C_uH_2u-O-(C₃H₆-O-)_v(C₂H₄-O-)_w-R³⁰     (XXX),
    
            CH₂=CH-CH₂-O-(C₃H₆-O-)_v(C₂H₄-O-)_w-R³⁰     (XXXI),
    
            CH₂=CH-CH₂-O-(C₃H₆-O-)_v(C₂H₄-O-)_w-SO₃M     (XXXII),
    
            [R³¹-O-(C₃H₆-O-)_v(C₂H₄-C)_w]_t-R³²     (XXXIII),
    
    in which R²⁰ and R²¹, independently of one another, are hydrogen or C₁-C₄-alkyl, preferably hydrogen or methyl,
    R²² is C₆-C₃₀-alkyl, C₆-C₃₀-alkenyl or C₇-C₃₀-alkylaryl, preferably C₈-C₂₄-alkyl,
    M is an alkali metal cation, an ammonium ion or hydrogen, preferably a sodium ion or an ammonium ion, R²⁵, R²⁶ and R²⁷, independently of one another, are hydrogen, C₁-C₃₀-alkyl, C₂-C₃₀-alkenyl, cycloalkyl, aryl or acyl, preferably hydrogen, C₁-C₂₄-alkyl or C₂-C₄-alkenyl,
    n and m, independently of one another, are integers from 1 to 4, preferably 2,
    p is an integer from 2 to 4, preferably 2,
    q is an integer from 1 to 100, preferably from 4 to 20,
    
    R²⁴ is hydrogen, C₁-C₃₀-alkyl, C₂-C₃₀-alkenyl, cycloalkyl, aryl or acyl, preferably C₁-C₁₈-alkyl,
    r is an integer from 0 to 100, preferably from 2 to 20,
    R²⁸ is C₂-C₄-alkenyl, preferably vinyl, allyl or methylvinyl,
    s is an integer from 0 to 100, preferably from 2 to 20,
    t is 1 or 2,
    
    R²⁹ is C₁-C₃₀-alkyl, preferably C₁-C₄-alkyl,
    u is an integer from 1 to 20, preferably from 2 to 10,
    v and w, independently of one another, are integers from 0 to 100, preferably from 2 to 20, at least one of the numbers v or w not being equal to zero,
    R³⁰ is hydrogen or C₁-C₄-alkyl, preferably hydrogen or methyl,
    R³¹ is an alkenyl radical or a carboxyalkenyl radical having 6 to 30 carbon atoms and
    R³² is hydrogen, C₁-C₄-alkyl or a radical of the formula PO_4-tM_3-t.
15. The composition as claimed in claim 14, wherein component D) is derived from compounds of the formula XVa

    

    in which q, R²² and M has the meaning defined in claim 14.
16. The composition as claimed in any of claims 1 to 15, which contains at least one nonionic emulsifier.
17. The use of the composition as claimed in any of claims 1 to 16 containing a mineral filler, the proportion of particles having a diameter of at least 40 µm being at least 40% by weight, as plaster and render.
18. The use of the composition as claimed in any of claims 1 to 16 containing a mineral filler, the mean diameter of the particles being from 1 to 40 µm, as paint, in particular as facade paint or as roofing tile paint.
19. The use of plastics dispersions containing an aqueous polymer dispersion prepared by free radical emulsion polymerization and derived from the monomers A), B), C), optionally D) and optionally E) as claimed in claim 1 and colloidal silica in plasters and renders or in paints.
20. Aqueous plastics dispersion containing

    a) a copolymer which is prepared by emulsion polymerization and is derived from

    A) at least 40% by weight, based on the total amount of monomers, of vinyl esters of saturated carboxylic acids, optionally vinylaromatic monomers and/or optionally esters of α,β-unsaturated carboxylic acids,

    B) from 0.1 to 10% by weight, based on the total amount of monomers, of α,β-ethylenically unsaturated mono- and/or dicarboxylic acids and/or of α,β-ethylenically unsaturated sulfonic acids and/or of α,β-ethylenically unsaturated phosphoric acids and/or of α,β-ethylenically unsaturated phosphonic acids and/or of amides of α,β-ethylenically unsaturated mono- and/or dicarboxylic acids,

    C) from 0.5 to 15% by weight, based on the total amount of monomers, of ethylenically unsaturated monomers which have at least one alkoxysilyl group,

    D) optionally up to 10% by weight, based on the total amount of monomers, of an ethylenically unsaturated monomer which contains an anionic and/or nonionic emulsifying group and

    E) optionally up to 20% by weight, based on the total amount of monomers, of other monomers copolymerizable with the monomers of groups A), B), C) and optionally D), with the proviso that,
    instead of or in addition to the copolymerization of the monomer C), from 0.5 to 15% by weight, based on the total amount of monomers, of a monomer which has at least one amino,
    mercapto or epoxide group in addition to at least one alkoxysilyl group is added after the emulsion polymerization, and

    b) colloidal silica.
21. The aqueous plastics dispersion as claimed in claim 20, which is derived from monomers A), B), C), D), and optionally E).
22. The aqueous plastics dispersion as claimed in either of claims 20 and 21, wherein the following monomer mixtures are used as monomers A): vinyl acetate/vinyl chloride/ethene, vinyl acetate/vinyl laurate/ethene, vinyl acetate/vinyl versatate/2-ethylhexyl acrylate, vinyl acetate/vinyl laurate/ethene/vinyl chloride, vinyl acetate/vinyl versatate/ethene/vinyl chloride, vinyl versatate/ethene/vinyl chloride, vinyl acetate/vinyl versatate, vinyl acetate/vinyl versatate/ethene and vinyl acetate/ethene, the combination vinyl acetate/ethene being particularly preferred.

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